CN102583580B - Method for preparing high-purity cobalt nitrate crystals from Co/SiO2 waste catalysts - Google Patents
Method for preparing high-purity cobalt nitrate crystals from Co/SiO2 waste catalysts Download PDFInfo
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- C22B23/04—Obtaining nickel or cobalt by wet processes
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Abstract
The invention discloses a method for preparing high-purity cobalt nitrate crystals from Co/SiO2 waste catalysts. The method sequentially comprises the following steps of: 1) calcining Co/SiO2 waste catalysts to be treated at 350 to 500 DEG C under the existence of air, cooling the Co/SiO2 waste catalysts to the room temperature, and grinding the Co/SiO2 waste catalysts into powder; 2) transferring the Co/SiO2 waste catalyst powder into a fluidized bed reactor, and taking reduction reaction for 8 to 12 hours in mixed gas of H2 and N2; 3) adding the waste catalysts subjected to the reduction reaction into excessive dilute nitric acid solution to be fully dissolved and filtered; 4) using alkali liquor for regulating the pH value of the obtained cobalt nitrate solution to 1.5, adding oxalic acid solution for reaction under the water bath condition of 25 to 80 DEG C, regulating the pH value of the reacted solution to 1.5 by diluted alkali solution, and filtering the materials when the materials are still hot to obtain cobalt oxalate precipitates; 5) drying the cobalt oxalate precipitates, and then roasting the dried cobalt oxalate precipitates under the temperature condition of 550 to 650 DEG C for 4 to 8 hours; 6) dissolving the obtained cobalt oxide by diluted nitric acid solution; and 7) carrying out evaporation crystallization on the cobalt nitrate solution to obtain Co(NO3)2 6H2O crystals. Practice proves that the recovery rate and the product purity of the Co(NO3)2 6H2O in the method are high.
Description
Technical field
The invention belongs to the preparing technical field of inorganics, specifically refer to a kind of Co/SiO of utilization
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal.
Technical background
Along with petering out of the day by day serious and petroleum resources of environmental pollution, developing pollution-free, reproducible new forms of energy becomes the focus that people study.Biomass are renewable resourcess abundant, the most cheap on the earth, and the lignocellulose biomass that the whole world produces by photosynthesis is every year up to 1,500 hundred million tons, and wherein 90% left and right is at present not yet by human use.Biogas is changed into synthetic gas, then by Fischer-Tropsch synthesis, generate synthetic oil, this synthetic oil, through postprocessing working procedures such as following process, rectifying, can obtain being better than the super clean petrol and diesel oil of Europe V standard, is with a wide range of applications.
Silica supported cobalt-based Co/SiO
2catalyst to catalyzing hydrogenating activity is high, and speed of reaction is not subject to the impact of water partial pressure, is difficult for carbon distribution and poisoning, and generates CO
2selectivity low, the selectivity of long chain hydrocarbon is high, in product, oxygenatedchemicals is less, be in current Fischer-Tropsch synthesis industry preferably and study more catalyst system.China's cobalt ore resource is most deficient, 2% of the not enough world of explored allowable exploitation allowable exploitation, and a year usage quantity approaches 25% of world's total amount consumed, so the serious dependence on import of the cobalt resource of China, expensive, finally cause catalyzer cost higher.Synthetic with reclaiming cobalt spent catalyst from co-based fischer-tropsch, for cobalt-base catalyst, produce again, not only reduced the pollution of spent catalyst to environment, improved the utilization ratio of cobalt resource, and greatly reduce the production cost of cobalt catalyst, there is good environment benefits and economic gains.
Before the present invention, the Chinese patent that application number is 200810055107.0 discloses the recovery method of cobalt in a kind of Co based Fischer-Tropsch synthesis catalyst, by deionized water with containing cobalt Fischer-Tropsch spent catalyst, (comprises with SiO
2, Al
2o
3, ZrO
2, TiO
2for carrier containing cobalt spent catalyst) be to add in reactor at 1~5: 1 by weight, CO gas is passed into reactor, heating constant temperature react; Then lower the temperature CO gas is emitted from reactor, after from reactor, water (cobalt-carrying solution) being discharged, in water, add alkali lye solution, make cobalt be precipitated as Co (OH)
2; In precipitation, add nitric acid dissolve, evaporative crystallization, obtains Co (NO
3)
26H
2o.The method is first to obtain Co (OH)
2precipitation, then uses dilute nitric acid dissolution, the Co (NO of gained
3)
26H
2o purity is lower can only be below 98%.Application number is that 200910272794.6 Chinese patent discloses a kind of method of utilizing used for Fischer-Tropsch synthesis alumina load cobalt-based spent catalyst to prepare high pure nitric acid cobalt, this method comprise mill, the step such as concentrated hydrochloric acid dissolves, the heavy cobalt of sodium sulphite, the heavy cobalt of oxalic acid, calcining, nitric acid dissolve, evaporative crystallization, the Co (NO finally obtaining
3)
26H
2o purity is up to more than 99%, but due to the method not to spent catalyst reduce process and removal process in the intermediate product CoS crystal grain that generates very thin, filtration difficulty, easily loses cobalt, thereby causes the rate of recovery of cobalt to reduce, and is 92% left and right.
Summary of the invention
Object of the present invention is exactly that the Co/SiO that utilizes that a kind of rate of recovery is high, product purity is high will be provided
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal.
For achieving the above object, the Co/SiO that utilizes provided by the invention
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, comprises the steps:
1) by pending Co/SiO
2spent catalyst is roasting 3~6h under 350~500 ℃ of conditions that have an air, is cooled to grind into powder after room temperature;
2) the spent catalyst powder after calcination process is proceeded to fluidized-bed reactor, at H
2, N
2in mixed gas, carry out reduction reaction 8~12h, wherein, control H in described mixed gas
2, N
2long-pending ratio is 1~4: 1;
3) spent catalyst through reduction reaction is added in excessive dilute nitric acid solution and fully dissolves, filters, obtain cobalt nitrate solution;
4) with alkali lye, regulate the pH value to 1.5 of resulting cobalt nitrate solution, under 25~80 ℃ of water bath condition, add and be preheated to the oxalic acid solution that 25~80 ℃ and pH value are 1.5 and react, after regulating reaction with dilute alkaline soln, solution is to pH value=1.5, filtered while hot obtains cobalt oxalate precipitation, uses deionized water wash cobalt oxalate precipitation, until filtrate is neutral, wherein, the molar content of controlling add of oxalic acid solution mesoxalic acid is 2~3 times of cobalt molar content in cobalt nitrate solution;
5) after cobalt oxalate precipitation is dry, in temperature, be to calcine 4~8h under 550~650 ℃ of conditions, cobalt oxalate divides and solves cobalt oxide;
6) gained cobalt oxide is dissolved with dilute nitric acid solution, again obtain cobalt nitrate solution;
7) described cobalt nitrate solution evaporative crystallization is obtained to Co (NO
3)
26H
2o crystal.
During reduction reaction further, step 2), the flow velocity of controlling described gas mixture is 1000~4000h
-1, in reactor, pressure is 0.1~1MPa, temperature of reaction is 350~750 ℃.
Again further, it is 1~3mol/L that the concentration of rare nitric acid step 3) is controlled.
Further, it is 1~3mol/L that dilute nitric acid solution concentration step 6) is controlled.
Also further, step 4) it is 70 ℃ that bath temperature described in is controlled, and described oxalic acid solution is preheated to 70 ℃, and described washing is preheated to 70 ℃ with deionized water.
The present invention utilizes used for Fischer-Tropsch synthesis Co/SiO
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, and the heavy hydrocarbon by aerobic roasting Removal of catalyst particle surface, then carries out reduction reaction by expense catalyzer by reductibility mixed gas, and the H in gas mixture while controlling reduction reaction
2volume fraction, more than 50%, can make the cobalt in spent catalyst be reduced fully, then adopts excessive rare nitric acid that the reduzate of catalyzer is fully dissolved to obtain to cobalt nitrate solution.Then, cobalt nitrate solution and oxalic acid solution are fully reacted to oxalic cobalt precipitation, in this step reaction, control the excessive cobalt that is conducive to of oxalic acid and precipitate completely, improve the transformation efficiency of cobalt; And in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and oxalic acid reaction process, strictly control the pH value of solution 1.5, because only under this pH value, just can guarantee that cobalt oxalate is precipitated out completely; During reaction, the control of the temperature of solution is 25~80 ℃, is preferably and is controlled at 70 ℃, and too low because if temperature is controlled, the cobalt oxalate particle of generation is partially thin, can in follow-up filtration and washing step, cause greater loss; Because this reaction is in oxalic cobalt precipitation, the hydrogen ion discharging reduces pH, in order to make cobalt precipitation completely, during reaction end must by the conciliation of pH value be controlled at 1.5.Then under hot conditions, cobalt oxalate is decomposed and generates cobalt oxide, cobalt oxide obtains cobalt nitrate solution after being dissolved in rare nitric acid again, finally this solution evaporation crystallization is obtained to highly purified Co (NO
3)
26H
2o crystal.
The present invention is by the strict processing condition of controlling in reaction process, and not only the rate of recovery is high to make products obtained therefrom, and purity is high, and product can be directly used in the fischer-tropsch synthetic catalyst production of biomass indirect liquefaction synthetic oil processed.And the inventive method is simple to operate, flow process is short, low to equipment and process conditional request, is suitable for heavy industrialization application.
Embodiment
Below in conjunction with specific embodiment, the present invention is utilized to Co/SiO
2the method that spent catalyst is prepared high pure nitric acid cobalt crystal is described in further detail:
Embodiment 1
1) get useless Co/SiO
2granules of catalyst 20.01g, results of elemental analyses is: containing cobalt 12.1%; Pack retort furnace into, pass into air, from room temperature start program, be warming up to 350 ℃ and constant temperature 6 hours, the heavy hydrocarbon of Removal of catalyst particle surface, is then cooled to room temperature, by the cooling rear taking-up of the powder material after roasting, grinds to form uniform powder;
2) spent catalyst powder is transferred in fluidized-bed reactor, at 400 ℃, 1MPa, H
2/ N
2gas mixture (H wherein
2, N
2long-pending ratio is 1: 1), air speed is 4000h
-1condition under reduce 10h;
3) spent catalyst through reduction reaction is added to the abundant stirring and dissolving of rare nitric acid that 200ml concentration is 3mol/L, filters and remove insolubles, the filtrate obtaining is cobalt nitrate solution;
4) with saturated NaOH solution, regulate cobalt nitrate solution pH value to 1.5; Choose 12.95g oxalic acid solid (H
2c
2o
42H
2o) adding deionized water just all dissolves it, the NaOH solution that is 1% with weight percent is adjusted to pH=1.5, obtain oxalic acid solution, oxalic acid solution is preheated to 70 ℃, and in cobalt nitrate solution, dripping (0.01mL/s) oxalic acid solution under 70 ℃ of water bath condition, limit edged constantly stirs, and is added dropwise to complete rear continuation and keeps stirring 15min, the NaOH solution that is 5% with weight percent regulates reaction end solution to pH=1.5, and filtered while hot obtains CoC
2o
4precipitation; Deionized water wash CoC with 70 ℃
2o
4precipitation, until filtrate is neutrality;
5) CoC above-mentioned steps being obtained
2o
4after precipitation is dry, proceeds in retort furnace and calcine 5h at 550 ℃, obtain Co
2o
3;
6) gained cobalt oxide is added 3mol/L salpeter solution it is just dissolved completely, again obtain cobalt nitrate solution;
7) cobalt nitrate solution is placed in to 70 ℃ of water-bath evaporation concentration, while there is crystalline film to solution surface, takes off at once, and keep stirring, until crystallization completes, go to quality in moisture eliminator and keep constant weight, obtain Co (NO
3)
26H
2the quality of O is 11.57g.
The method providing according to GBT 15898-1995 records Co (NO in product
3)
26H
2o purity is 99.40%, and the rate of recovery of the present embodiment cobalt is 96.18%.
Embodiment 2
1) get useless Co/SiO
2granules of catalyst 10.24g, results of elemental analyses is: containing cobalt 18.36%; Pack retort furnace into, pass into air, from room temperature start program, be warming up to 400 ℃ and constant temperature 4 hours, with the heavy hydrocarbon of Removal of catalyst particle surface, be then cooled to room temperature, by the cooling rear taking-up of the spent catalyst after roasting, grind to form uniform powder;
2) spent catalyst powder is transferred in fluidized-bed reactor, at 750 ℃, 0.5MPa, H
2/ N
2gas mixture (H wherein
2, N
2long-pending ratio is 3: 1), air speed is 3000h
-1condition under reduce 8h;
3) spent catalyst through reduction reaction is added to the abundant stirring and dissolving of rare nitric acid that 160mL concentration is 2mol/L, filters and remove insolubles, the filtrate obtaining is cobalt nitrate solution;
4) with saturated NaOH solution, regulate cobalt nitrate solution pH to 1.5; Choose 10.05g oxalic acid solid (H
2c
2o
42H
2o) adding deionized water just all dissolves, with the sodium hydroxide solution that weight percent is 1%, be adjusted to pH=1.5, obtain oxalic acid solution, oxalic acid solution is preheated to 70 ℃, and in cobalt nitrate solution, dripping (0.01mL/s) oxalic acid solution under 70 ℃ of water bath condition, limit edged constantly stirs, and is added dropwise to complete rear continuation and keeps stirring 15min, the NaOH solution that is 5% with weight percent regulates terminal to pH=1.5, and filtered while hot obtains CoC
2o
4precipitation; Deionized water wash CoC with 70 ℃
2o
4precipitation, until filtrate is neutrality;
5) CoC above-mentioned steps being obtained
2o
4after dry, proceed in retort furnace and calcine 4h at 650 ℃, obtain Co
2o
3;
6) by gained Co
2o
3add the salpeter solution of 3mol/L that it is just dissolved completely, again obtain cobalt nitrate solution;
7) cobalt nitrate solution is placed in to 70 ℃ of water-bath evaporation concentration, while there is crystalline film to solution surface, takes off at once, and keep stirring, until crystallization completes, go to quality in moisture eliminator and keep constant weight, obtain Co (NO
3)
26H
2the quality of O is 9.04g.
The method providing according to GBT 15898-1995 records Co (NO in product
3)
26H
2o purity is 99.57%, and the rate of recovery of the present embodiment cobalt is 96.94%.
Embodiment 3
1) get useless Co/SiO
2granules of catalyst 15.62g, results of elemental analyses is: containing cobalt 22.64%; Pack retort furnace into, pass into air, from room temperature start program, be warming up to 500 ℃ of constant temperature 3 hours, with the heavy hydrocarbon of Removal of catalyst particle surface, be then cooled to room temperature; By the cooling rear taking-up of the spent catalyst after roasting, grind to form uniform powder;
2) spent catalyst powder is transferred in fluidized-bed reactor, at 600 ℃, 0.1MPa, H
2/ N
2gas mixture (H wherein
2, N
2long-pending ratio is 4: 1), air speed is 1000h
-1condition under reduce 12h;
3) spent catalyst through reduction reaction is added to the abundant stirring and dissolving of rare nitric acid that 300mL concentration is 1mol/L, filters and remove insolubles, the filtrate obtaining is cobalt nitrate solution;
4) with NaOH solution, regulate cobalt nitrate solution pH to 1.5.Choose 18.91g oxalic acid solid (H
2c
2o
42H
2o) add deionized water to just all dissolving, with the sodium hydroxide solution that weight percent is 1%, be adjusted to pH=1.5, obtain oxalic acid solution, oxalic acid solution is preheated to 70 ℃, and in cobalt nitrate solution, dripping (0.01mL/s) oxalic acid solution under 70 ℃ of water bath condition, limit edged constantly stirs, and is added dropwise to complete rear continuation and keeps stirring 15min, the NaOH solution that is 5% with weight percent regulates terminal to pH=1.5, and filtered while hot obtains CoC
2o
4precipitation; Deionized water wash CoC with 70 ℃
2o
4precipitation, until filtrate is neutrality;
5) CoC above-mentioned steps being obtained
2o
4after dry, proceed in retort furnace and calcine 8h at 600 ℃, obtain Co
2o
3;
6) by gained Co
2o
3add 1mol/L concentrated nitric acid solution that it is just dissolved completely, again obtain cobalt nitrate solution;
7) cobalt nitrate solution is placed in to 70 ℃ of water-bath evaporation concentration, while there is crystalline film to solution surface, takes off at once, and keep stirring, until crystallization completes, go to quality in moisture eliminator and keep constant weight, obtain Co (NO
3)
26H
2the quality of O is 16.94g.
It is 99.63% that the method providing according to GBT 15898-1995 records product moderate purity, and the rate of recovery of the present embodiment cobalt is 96.64%.
Embodiment 4
1) get useless Co/SiO
2granules of catalyst 15.62g, results of elemental analyses is: containing cobalt 22.64%; Pack retort furnace into, pass into air, from room temperature start program, be warming up to 450 ℃ of constant temperature 5h, with the heavy hydrocarbon of Removal of catalyst particle surface, be then cooled to room temperature; By the cooling rear taking-up of the spent catalyst after roasting, grind to form uniform powder;
2) spent catalyst powder is transferred in fluidized-bed reactor, at 350 ℃, 0.3MPa, H
2/ N
2gas mixture (H wherein
2, N
2long-pending ratio is 3: 1), air speed is 3000h
-1condition under reduce 10h;
3) spent catalyst through reduction reaction is added to the abundant stirring and dissolving of rare nitric acid that 300mL concentration is 1mol/L, filters and remove insolubles, the filtrate obtaining is cobalt nitrate solution;
4) with NaOH solution, regulate cobalt nitrate solution pH to 1.5.Choose 22.12g oxalic acid solid (H
2c
2o
42H
2o) add deionized water to just all dissolving, with the sodium hydroxide solution that weight percent is 1%, be adjusted to pH=1.5, obtain oxalic acid solution, oxalic acid solution is preheated to 80 ℃, and in cobalt nitrate solution, dripping (0.01mL/s) oxalic acid solution under 80 ℃ of water bath condition, limit edged constantly stirs, and is added dropwise to complete rear continuation and keeps stirring 15min, the NaOH solution that is 5% with weight percent regulates terminal to pH=1.5, and filtered while hot obtains CoC
2o
4precipitation; Deionized water wash CoC with 70 ℃
2o
4precipitation, until filtrate is neutrality;
5) CoC above-mentioned steps being obtained
2o
4after dry, proceed in retort furnace and calcine 6h at 600 ℃, obtain Co
2o
3;
6) by gained Co
2o
3add 1mol/L concentrated nitric acid solution that it is just dissolved completely, again obtain cobalt nitrate solution;
7) cobalt nitrate solution is placed in to 70 ℃ of water-bath evaporation concentration, while there is crystalline film to solution surface, takes off at once, and keep stirring, until crystallization completes, go to quality in moisture eliminator and keep constant weight, obtain Co (NO
3)
26H
2the quality of O is 17.32g.
It is 99.55% that the method providing according to GBT 15898-1995 records product moderate purity, and the rate of recovery of the present embodiment cobalt is 97.04%.
Claims (9)
1. one kind is utilized Co/SiO
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: it comprises the steps:
1) by pending Co/SiO
2spent catalyst is roasting 3~6h under 350~500 ℃ of conditions that have an air, is cooled to grind into powder after room temperature;
2) spent catalyst after calcination process is proceeded to fluidized-bed reactor, at H
2, N
2in mixed gas, carry out reduction reaction 8~12h, wherein, control H in described mixed gas
2, N
2long-pending ratio is 1~4: 1;
3) spent catalyst through reduction reaction is added in excessive dilute nitric acid solution and fully dissolves, filters, obtain cobalt nitrate solution;
4) with alkali lye, regulate the pH value to 1.5 of resulting cobalt nitrate solution, under 25~80 ℃ of water bath condition, add and be preheated to the oxalic acid solution that 25~80 ℃ and pH value are 1.5 and react, after regulating reaction with dilute alkaline soln, solution is to pH value=1.5, filtered while hot obtains cobalt oxalate precipitation, uses deionized water wash cobalt oxalate precipitation, until filtrate is neutral, wherein, the molar content of controlling add of oxalic acid solution mesoxalic acid is 2~3 times of cobalt molar content in cobalt nitrate solution;
5) after cobalt oxalate precipitation is dry, in temperature, be to calcine 4~8h under 550~650 ℃ of conditions, obtain cobalt oxide;
6) gained cobalt oxide is dissolved with dilute nitric acid solution, again obtain cobalt nitrate solution;
7) described cobalt nitrate solution evaporative crystallization is obtained to Co (NO
3)
26H
2o crystal.
2. the Co/SiO that utilizes according to claim 1
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 2) described in during reduction reaction, the flow velocity of controlling gas mixture is 1000~4000h
-1, the pressure of reactor is 0.1~1MPa, temperature of reaction is 350~750 ℃.
3. the Co/SiO that utilizes according to claim 1 and 2
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 3) described in the concentration of rare nitric acid to control be 1~3mol/L.
4. the Co/SiO that utilizes according to claim 1 and 2
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 6) described in the concentration of dilute nitric acid solution to control be 1~3mol/L.
5. the Co/SiO that utilizes according to claim 3
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 6) described in the concentration of dilute nitric acid solution to control be 1~3mol/L.
6. the Co/SiO that utilizes according to claim 1 and 2
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 4) described in bath temperature to control be 70 ℃, described oxalic acid solution is preheated to 70 ℃, described washing is preheated to 70 ℃ with deionized water.
7. the Co/SiO that utilizes according to claim 3
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 4) described in bath temperature to control be 70 ℃, described oxalic acid solution is preheated to 70 ℃, described washing is preheated to 70 ℃ with deionized water.
8. the Co/SiO that utilizes according to claim 4
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 4) described in bath temperature to control be 70 ℃, described oxalic acid solution is preheated to 70 ℃, described washing is preheated to 70 ℃ with deionized water.
9. the Co/SiO that utilizes according to claim 5
2spent catalyst is prepared the method for high pure nitric acid cobalt crystal, it is characterized in that: step 4) described in bath temperature to control be 70 ℃, described oxalic acid solution is preheated to 70 ℃, described washing is preheated to 70 ℃ with deionized water.
Priority Applications (20)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210055799.5A CN102583580B (en) | 2012-03-05 | 2012-03-05 | Method for preparing high-purity cobalt nitrate crystals from Co/SiO2 waste catalysts |
BR112014021849-8A BR112014021849B1 (en) | 2012-03-05 | 2013-03-04 | METHOD FOR PREPARING HIGH PURITY COBALT NITRATE CRYSTALS FROM CO / SIO2 CATALYST WASTE |
MYPI2014002570A MY157636A (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
MX2014010568A MX355250B (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts. |
AP2014007987A AP2014007987A0 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crysatls from CO/SIO2 waste catalysts |
AU2013230404A AU2013230404B2 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from Co/SiO2 waste catalysts |
HUE13757151A HUE036070T2 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
PCT/CN2013/072109 WO2013131452A1 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
JP2014560229A JP5837998B2 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high purity cobalt nitrate crystals using CO / SIO2 waste catalyst |
RU2014140152/05A RU2580744C1 (en) | 2012-03-05 | 2013-03-04 | METHOD OF PRODUCING COBALT NITRATE CRYSTALS OF HIGH PURITY FROM DEAD CATALYST Co/SiO2 |
SG11201405384YA SG11201405384YA (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
KR1020147027913A KR101567589B1 (en) | 2012-03-05 | 2013-03-04 | METHOD FOR PREPARING HIGH-PURITY COBALT NITRATE CRYSTALS FROM Co/SiO2 WASTE CATALYSTS |
SI201330896T SI2824075T1 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
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EP13757151.9A EP2824075B1 (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
DK13757151.9T DK2824075T3 (en) | 2012-03-05 | 2013-03-04 | PROCEDURE FOR MANUFACTURING HIGH PURITY OF COBAL NITRATE CRYSTALS FROM CO / SIO2 WASTE CATALOGS |
CA2866188A CA2866188C (en) | 2012-03-05 | 2013-03-04 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
US14/477,909 US8986644B2 (en) | 2012-03-05 | 2014-09-05 | Method for preparation of high purity, crystalline cobalt nitrate from spent cobalt/silica catalyst |
ZA2014/07150A ZA201407150B (en) | 2012-03-05 | 2014-10-02 | Method for preparing high-purity cobalt nitrate crystals from co/sio2 waste catalysts |
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CN101700913A (en) * | 2009-11-17 | 2010-05-05 | 中南民族大学 | Method for preparing high-purity cobalt nitrate by utilizing alumina-supported cobalt-based spent catalyst for Fischer-Tropsch synthesis |
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SI2824075T1 (en) | 2018-05-31 |
EP2824075A1 (en) | 2015-01-14 |
ZA201407150B (en) | 2015-11-25 |
AU2013230404A1 (en) | 2014-10-16 |
EP2824075A4 (en) | 2015-11-18 |
US20140377153A1 (en) | 2014-12-25 |
AP2014007987A0 (en) | 2014-10-31 |
MX2014010568A (en) | 2014-12-08 |
AU2013230404B2 (en) | 2015-02-19 |
CA2866188C (en) | 2017-04-18 |
CA2866188A1 (en) | 2013-09-12 |
HUE036070T2 (en) | 2018-06-28 |
WO2013131452A1 (en) | 2013-09-12 |
KR20140130748A (en) | 2014-11-11 |
MY157636A (en) | 2016-07-15 |
SG11201405384YA (en) | 2014-10-30 |
JP5837998B2 (en) | 2015-12-24 |
RU2580744C1 (en) | 2016-04-10 |
MX355250B (en) | 2018-04-11 |
JP2015515362A (en) | 2015-05-28 |
HRP20171983T1 (en) | 2018-02-23 |
DK2824075T3 (en) | 2018-01-15 |
EP2824075B1 (en) | 2017-10-11 |
BR112014021849B1 (en) | 2020-12-15 |
IN2014MN01922A (en) | 2015-07-10 |
KR101567589B1 (en) | 2015-11-09 |
US8986644B2 (en) | 2015-03-24 |
CN102583580A (en) | 2012-07-18 |
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